AbstractFor semiempirical SCF MO methods based on the NDDO assumption, the so-called one-center hy-brid integrals of the type (ab/cd) are required, These integrals are expressed in terms of theSlater-Condon parameters (scp) Rk(abcd) with different radial functions. The SCPsfrom atomicspectra are evaluated by taking into account configurational interaction (CI).As an example, the R1(sdpp),R2(sdpp), and R2(sddd) sCPsfor Ti I, Ti II, and Ti III have been evaluated and the valuesof these parameters are compared with those calculated with Slater-type orbitals. 1. Introduction One of the main features of the modern semiempirical SCFMOtheories is theapproximation of one-center integrals by certain quantities estimated from spec-troscopic data [1]. These parameters are evaluated in the following way: Thespectroscopic energy term of an atom according to Slater-Condon theory basedon the central-field approximation is expressed as a linear function of the Fk and Gk Slater-Condon parameters (scp) [2]. The sCPsare the radial parts of theCoulomb and exchange integrals of electronic interaction. Hence, one can obtainthe semiempirical one-center integrals by least-squares' fitting of the availablespectroscopic data to the theoretical equations.The semiempirical integrals obtained in [3] are sufficient to construct thesemiempirical methods in CNDO,INDO,and NDDOapproximations [4]for